The application is the Chinese patent application 201480063810.X (PCT/ for the applying date being on November 24th, 2014
EP2014/075402 divisional application).
Summary of the invention
By providing method described below and defined in the claims, the skill to solve the above problems is realized
Art scheme.
Therefore, the present invention provides the methods for preparing antireflective coating compositions comprising following steps:
1) such as get off to prepare emulsion oil-in-water by mixing:
Nonpolar organic compound A;
Cationic addition copolymer as emulsion stabilizer;With
The aqueous medium of pH 2-6;
Mass ratio C/A is 0.1 to 2, to obtain the cream that the particle size of 1-50 mass % (based on lotion) is 30-300nm
Change drop;And
2) it is mentioned by adding at least one precursors of inorganic oxides to the lotion obtained in step 1) to emulsion droplet
For inorganic oxide shell, to obtain the organic/inorganic core-shell nanoparticles that core shell mass ratio is 0.2 to 25.
Using method of the invention, discovery can prepare the coating composition comprising the core-shell particles based on emulsion droplet,
The emulsion droplet includes liquid nonpolar organic compound and with the particle size within the scope of 30 to 300nm.The particle ruler
It is very little can by the type of organic compound and the monomer composition of cationic copolymer and/or by alternative condition such as temperature,
The stirring rate of pH, aqueous medium composition and lower degree are controlled.Another advantage of the method for the present invention is to be obtained
The dispersion of the core-shell nanoparticles obtained is stable at different conditions;Its pot-life or period of storage are improved, and is permitted
Perhaps for example change its concentration and dicyandiamide solution, and adhesive and helper component that addition is different.Using side according to the present invention
The coating composition that method obtains can be advantageously used at a temperature of wide scope in different substrate materials (including with low durothermic
Thermoplastic matrix) on prepare porous ARC;Because organic compound can pass through solvent extraction at relatively low temperatures or steaming
Hair is easily removed from core-shell particles, and low-temperature curable adhesive can be used.
It according to the method for the present invention include step 1), wherein nonpolar organic compound A;Cationic addition copolymer C;One
The aqueous medium of quantitative pH 2-6 is mixed with 0.1 to 2 mass ratio C/A, to prepare emulsion oil-in-water.In order to prepare water packet
Water emulsion, " nonpolar organic compound A " used herein be higher than 0 DEG C, be preferably higher than 10 or 20 DEG C at a temperature of
Usually liquid.Compound A preferably retains liquid under conditions of preparing lotion and in subsequent technique and storage steps
Body characteristics.On the other hand, it is advantageous that when preparing ARC by composition, especially in curing schedule, can be held by evaporation
It changes places from coating removal compound A, to generate porosity.Therefore, compound A preferably has at least 30,40,60,80 or 100
DEG C and at most 350,300,250,200 or 150 DEG C of boiling point.
Compound A used according to the method for the present invention has nonpolar (or hydrophobicity) feature, it means that its
There is at most 5kg/m at room temperature3Water in solubility, and be capable of forming the phase being separated from water.Compound A is preferably under
The compound that can be dispersed in water in the presence of copolymer C described in text.Preferably, compound A have at room temperature to
More 4,3,2 or 1kg/m3Water in solubility
It is highly preferred that compound A is non-polymeric." non-polymeric " is understood to herein, and A is not by more than 2
Repeated monomer unit building, as it have been discovered that being for unacceptable application, as compound A particularly with hot setting
It may be takeed a long time when being polymer from core-shell nanoparticles extraction or evaporated compounds A.
Compound A is preferably for being inert for other components used in method or composition of the invention.
In an operation ad hoc fashion according to the method for the present invention, the step of compound A can be with methodologies described hereinafter
3) added adhesive reaction in;Following situation is especially true: when in the aqueous medium of final coating composition and step 1)
Those of it is different and including, for example, more organic solvents, and compared with aqueous medium when preparing lotion, compound A exists
When wherein showing the solubility of enhancing.In this case, compound A can be from the core-shell particles dispersed by partly
It extracts in the also medium comprising adhesive.Compound A can for example be understood to when solidifying coating layer can with it is organic can
The unsaturated compound that polymeric binder reacts jointly.
The example of non-polar compound A includes hydrocarbon compound, fatty acid, alcohol, ester, ether, vinyl compound etc..Suitably
Example includes hexamethylene, decane, toluene, trimethylbenzene, isoamyl acetate, C8-C22 alcohol, styrene, (methyl) acrylic acid alkyl
Ester, butanediol dimethylacrylate, hexanediol dimethacrylate etc..
In the method according to the invention, a kind of compound can be used as compound A, but institute as above also can be used
The mixture of the compound of restriction.Also such compound A can be used, wherein having dissolved on a small quantity (is, for example, less than 4 or 2 weights
Measure %) the hydrophobic compound for being unsatisfactory for above-mentioned restriction, which can be with the dispersion of auxiliary compounds A.Properly
The example of mixture be the hexamethylene comprising 1 weight % heptadecane.
In step 1) according to the method for the present invention, emulsion oil-in-water is by compound A and cationic addition copolymerization
Object C preparation.Copolymer C includes at least one monomeric unit with cationic charge and at least one neutral or nonionic
The non-polar monomer that monomer, preferably its corresponding homopolymer show solubility or anhydrous middle solubility in limited water.Always
For body, cationic copolymer should have positive zeta potential.Preferably, cationic copolymer C is not readily dissolved in water, but tends to
Micellar aggregates are formed, this enhances its function as emulsion stabilizer.Copolymer can be random but it is also possible to be block
Copolymer may include phenylethylene, acrylic compounds, methacrylic, the alkene same clan and/or vinyl comonomer.?
In the context of the application, all these monomers are collectively referred to as ethylenically unsaturated monomer or vinyl monomer;This includes containing methyl-
Methacrylate of vinyl groups etc..In the art, acrylic compounds and methacrylic compounds are logical
Often it is collectively referred to as (methyl) acrylic monomer.Addition copolymer can be advantageously used well known by persons skilled in the art various
Polymerization technique is prepared by a large amount of suitable vinyl monomers;This provides various copolymer compositions.Suitable example packet
Include bulk polymerization, polymerisation in solution and the emulsion polymerization using radical initiator.Copolymer is preferably provided in aqueous Jie
Dispersion in matter can be obtained by the emulsion polymerization of selected monomer, can also be by acquisition of such as getting off: organic molten
It polymerize in agent, then disperses copolymer obtained in aqueous medium, and optionally neutralizes nonionic functional group;This
It is as known in the art.
JP2011111558 is not disclosed in core that (there are component A to fall into the scope of the present invention in core there are component A
It is interior), do not disclose yet disclosed in this invention component A effect, disclose only using polymer core.In addition, not having yet
The open emulsion stabilizer C in the form of cationic addition copolymer.
JP208274261 is taught in the description, and in the core of the core-shell particles of JP208274261, solvent can be with
There is or even substitute copolymer together in polymer.However, it is not disclosed in core with embodiment there are solvent,
The feelings that the polymer of type indicated in JP208274261 can be not present in core are not disclosed with embodiment specifically
Core-shell nanoparticles are prepared under condition.In addition, JP208274261 does not disclose the cream used in the form of cationic addition copolymer
Liquid stabilizer C.
In the method according to the invention, copolymer C is preferably the copolymer by obtaining as follows
At least one cation or alkaline monomer (M1), including having can be in conjunction with proton to subsequently form cation
The compound of the side group of group, such as with the monomer of tertiary amine group;
At least one neutral or non-ionic monomer (M2);Preferably its corresponding homopolymer is not readily dissolved in aqueous medium
Non-polar monomer;With
Optionally at least a kind of polarity, anionic property or acid monomer (M3).
Cationic comonomer M1 and optional M3 will will increase solubility and dispersibility of the copolymer in water-based system;
And water solubility can be reduced by nonpolarity or hydrophobic interaction, non-ionic monomer unit M2, and promote to form aggregation
With the activity as emulsion stabilizer or polymeric surfactant.Excessively high M2 amount can lead to copolymer in an aqueous medium not
Molten and/or precipitating.It is therefore preferred that the type and amount of selection comonomer, so that copolymer can be scattered in aqueous medium
Form colloid particle.It is one advantage of the present invention that the random copolymer of this monomer has been able to play in an aqueous medium
The effect of emulsion stabilizer;The more complex synthetic route of block copolymer is prepared without using.According to be emulsified
The composition of compound A and aqueous medium, those skilled in the art will also select suitable copolymer to form.
In one preferred embodiment, according to the method for the present invention used in copolymer C be by obtaining as follows
Copolymer:
At least one monomer M1 of 1-25 moles of %;
At least one monomer M2 of 50-99 moles of %;With
At least one monomer M3 of 0-25 moles of % (summation of M1, M2 and M3 add up to 100%).
If comonomer M3, especially anion M3 be used to prepare copolymer, to obtain that there is net positive charge
The dosage of ionic copolymer uses monomer M1, such as to use monomer M1 relative to the dosage of M3 molar excess.
Preferably, according to the method for the present invention used in copolymer be cationic copolymer by obtaining as follows:
At least one monomer M1 of 5-15 moles of %;
At least one monomer M2 of 75-95 moles of %;With
At least one monomer M3 of 0-10 moles of %.
In further preferred embodiment, according to the method for the present invention used in copolymer be by obtaining as follows
This cationic copolymer: at least 5, at least the one of 6,7,8,9 or 10 moles of % and at most 25,20,15,12 or 10 mole of %
Kind monomer M1;With at least one monomer M2, the amount of monomer M2 makes the summation of M1 and M2 be 100 moles of %.
It can be suitable for the cation for forming the copolymer C used according to the method for the present invention via addition polymerization
Monomer M1 includes the vinyl monomer with ammonia official's energy side base;It can be can be when forming copolymer or after forming copolymer
The non-ionic monomer being neutralized, the monomer with the ammonia functional group being neutralized or the second with permanent quaternary ammonium group
Alkenyl monomer.
The example for carrying the vinyl monomer of nonionic ammonia functional group includes (methyl) acrylic acid N, N- dimethylamino
Base ethyl ester, the own ester of (methyl) acrylic acid N, N- dimethylamino, (methyl) acrylic acid N, N- diethylamino ethyl ester, (methyl) third
Olefin(e) acid N- methyl-N- butyl-amino ethyl ester, (methyl) tbutylaminoethylacrylate, (methyl) acrylic acid N, N- dimethyl
Amino propyl ester, (methyl) acrylic acid 2- (1,1,3,3- tetramethyl butyl amino) ethyl ester, (methyl) propenoic acid beta-morpholino ethyl ester,
4- (β-acrylyl oxy-ethyl) pyridine, vinyl benzyl amine, ethenylphenyl amine, 2- vinylpyridine or 4-vinylpridine,
P- aminostyryl, dialkyl amido styrene (such as N, N- bis aminomethyl styrene), the diallylamine replaced, N-
(the first that vinylpiperidine, N- vinyl imidazole, N- Vinylimdozoline, N- vinyl pyrazoles, N- vinyl indoles, N- replace
Base) acrylamide (such as 2- (dimethylamino) ethyl (methyl) acrylamide, 2- (tert-butylamino) ethyl (methyl) acryloyl
Amine, 3- (dimethylamino) propyl (methyl) acrylamide, (methyl) acrylamide, N- aminoalkyl (methyl) acrylamide),
Vinyl ethers (such as 10- aminodecyl vinyl ethers, 9- aminoheptyl vinyl ethers, 6- (diethylamino) hexyl vinyl
Ether, 5- Aminopentyl vinyl ethers, 3- aminopropyl vinyl ether, 2- amino-ethyl vinyl ethers, 2- aminobutyl vinyl
Ether, 4- aminobutyl vinyl ethers, 2- dimethyl aminoethyl vinyl base ether, N- (3,5,5- triethyl group hexyl) amino-ethyl second
Alkene ether, N- Cyclohexylamino ethyl vinyl ether, N- t-butylamino ethyl vinyl ethers, N- methylaminoethyl vinyl
Ether, N-2- ethylhexylamino ethyl vinyl ether, N- t-octyl amino-ethyl vinyl ethers, β-pyrrolidines ethyl vinyl ether
Or (N- beta-hydroxyethyl-N- methyl) amino-ethyl vinyl ethers).The olefinic containing cyclic annular urea groups or thiourea can also be used not
It is saturated monomer, such as (methyl) acrylyl oxy-ethyl ethylidene-urea, (methyl) acrylyl oxy-ethyl ethylidene thiourea, (methyl)
Acrylamide ethylidene-urea, (methyl) acrylamide ethylidene thiourea etc..Preferred monomer is amino-functional (methyl)
Acrylate and (methyl) acrylamide;Especially (methyl) acrylic acid N, N ,-dialkyl aminoalkyl ester, more specifically methyl
Tbutylaminoethylacrylate, dimethylamine propyl ester, dimethylaminoethyl methacrylate
(DMAEMA) or diethyl aminoethyl methacrylate (DEAEMA), more preferably DMAEMA and DEAEMA.
The example of suitable and preferred Ml monomer given above can also by before the polymerization with for example acid, preferably
It is handled with organic acid such as carboxylic acid etc. and is used with its ionized form.
The suitable example of M1 monomer with permanent quaternary ammonium group includes methacrylamidopropyltrimethyl trimethyl ammonium chloride
(MAPTAC), dimethyl diallyl ammonium chloride (DADMAC), 2- trimethylethyl methacrylic acid ammonium chloride (TMAEMC) with
And replace the quaternary ammonium salt monomer of (methyl) acrylic acid and (methyl) acrylamide.
Suitably used neutrality in the copolymer used according to the method for the present invention can be being formed by addition polymerization
Or non-ionic monomer M2 includes various olefinic insatiable hungers and/or vinyl monomer, including various phenylethylenes, (methyl) acrylic acid
Class, olefines and/or vinyl comonomer.At least one monomer M1 is preferably hydrophobic.Preferably, cationic copolymer
Comprising a certain amount of water-insoluble or hydrophobic comonomer, will promote copolymer be not it is non-sufficiently water-soluble, thus aqueous
Colloid particle or aggregation are self-assembled into medium.It (may be needed based on information disclosed in this specification and experiment
The auxiliary of further experiment), and according to copolymer form (such as type and amount of M1 and M2), condition (such as solvent composition, temperature
Degree, pH) and compound A type, technical staff will select the content of suitable monomer combination and they.
Suitable styrene monomer M2 includes styrene, α-methylstyrene and other substituted styrene.Suitably
(methyl) acrylic monomer M2 includes (methyl) alkyl acrylate or (methyl) acrylate base ester, preferably (first
Base) acrylic acid C1-C18Arrcostab or (methyl) acrylic acid C1-C8Arrcostab, such as (methyl) methyl acrylate, (methyl) propylene
Acetoacetic ester, (methyl) butyl acrylate (all isomers), (methyl) isobutyl acrylate, (methyl) acrylic acid 2- ethyl hexyl
Ester, (methyl) isopropyl acrylate, (methyl) propyl acrylate (all isomers) or (methyl) isobornyl acrylate.It is optimal
(methyl) acrylic monomer of choosing includes methyl methacrylate (MMA), ethyl methacrylate (EMA), methacrylic acid
N-butyl (BMA).Similarly, N- alkyl (methyl) acrylamide is used as monomer M2.The other monomers that can be copolymerized with M1
It may also used as monomer M2, including butadiene;Vinyl monomer, such as vinyl chloride, vinyl laurate, vinyl alkyl ethers
Deng.
Also the various compounds that can be copolymerized with M1 and M2 can be used as monomer M3, including acrylonitrile, metering system
Nitrile;Vinyl monomer, such as vinyl pyrrolidone, vinyl esters (such as vinyl acetate or vinyl propionate etc.).It can also
The copolymer used according to the method for the present invention is prepared to use anionic property or acid monomer M3, as with suspension
The monomer of phosphoric acid, sulfuric acid or carboxylic acid group.Suitable monomer includes the vinyl monomer with carboxylic acid group, and example is olefinic insatiable hunger
With monocarboxylic acid and/or dicarboxylic acids (such as fumaric acid, itaconic acid, maleic acid), particular with (methyl) propylene of carboxylic acid group
Acrylic monomer (such as acrylic acid (AA), methacrylic acid (MAA) and β-carboxy ethyl acrylate).Contain anionic group and sun
The copolymer of ionic group is referred to alternatively as polyampholyte (polyampholyte).Intramolecular between ionic group and point
Interaction can enhance its effect for being used as emulsion stabilizer in the method for the invention between son.
In a preferred embodiment according to the method for the present invention, cationic copolymer is by obtaining as follows: 5-
At least one monomer M1 of 15 moles of % is formed selected from (methyl) acrylate by ammonia function with (methyl) acrylamide
Group;With at least one monomer M2 of 85-95 moles of %, it is selected from the group of (methyl) acrylic acid C1-C18 Arrcostab.
In a further preferred embodiment according to the method for the present invention, it is total to using the cation by obtaining as follows
Polymers: MMA of the dimethylaminoethyl methacrylate (DMAEMA) of 5-10 moles of % as monomer M1 and 90-95 moles of %
As monomer M2;Or the copolymer by preparing as follows: the different ice of acrylic acid of the DMAEMA and 88-95 moles of % of 5-12 moles of %
Piece ester (IBOA).
In the method according to the invention, the molal weight of copolymer C can change in a wide range.Typically, it is copolymerized
Object has the weight average molecular weight (Mw) of 1-500kDa (kg/mol), and preferably Mw is at least 2,5,10,15 or even 20kDa but extremely
More 250,200,150,100,50 or even 40kDa, so that the activity as emulsion stabilizer is best.The molal weight of copolymer
The polymethyl methacrylate of known molal weight can be used as reference substance by gel permeation chromatography (GPC) and use six
Fluorine isopropanol is determined as solvent.
In step 1) according to the method for the present invention, emulsion oil-in-water is by mixing in the aqueous medium of pH 2-6
Come what is prepared, aqueous medium is obtained polymerisable compounds A and copolymer C by existing organic and/or inorganic acid or buffer compounds.?
Within the scope of the pH, copolymer C will be with cationic charge, and M1 monomer has (neutralized) tertiary amine pendent group.It is mixed
The temperature of conjunction is not crucial, but usually environment temperature is to about 50 DEG C.
" aqueous medium " refers to aqueous liquid herein.Aqueous medium can also be comprising that can be dissolved in water other than water
In or at least one organic solvent miscible with water, such as alcohol, ketone, ester or ether.Example includes 1,4- dioxane, third
Ketone, diethacetic acid ester, propyl alcohol, ethyl alcohol, methanol, butanol, methyl ethyl ketone, methyl propyl ketone and tetrahydrofuran.It is preferred that
Ground, aqueous medium include water and rudimentary (C1-C8) fatty alcohol, such as methanol, ethyl alcohol, isopropanol or 1- methoxyl group propan-2-ol;More
Preferably ethyl alcohol or isopropanol.If there is organic solvent, then its dosage is selected so that compound A and copolymer C is insoluble, from
And ensure to be formed the emulsion droplet of compound A and copolymer C.The amount of preferably organic solvent be at most 10 mass %, more preferably
Ground at most 8,6 or 4 mass % (being based on total composition).Preferably, the solvent composition of aqueous medium is also apply to the resulting shell
In rear step 2).
In the method according to the invention, the addition manner of component A and C and sequence and the mode mixed with aqueous medium
It is not sequentially particularly critical.For example, compound A and copolymer C can be added simultaneously or sequentially be added, optionally stirring
Under.Can promote the formation of emulsion droplet by stirring, for example, with relatively low speed stirring rod, with super mixer,
With high pressure homogenisers or use ultrasonic method.Actual stirring rate (or when using replaceability mixing arrangement as exemplified above
Similar setting) can change, and if those of ordinary skill in the art are by carrying out the rate determined by routine experiment
Selection is to realize emulsion oil-in-water.
In the step of by mixed compound A in an aqueous medium and copolymer C to prepare emulsion oil-in-water, C and A
Mass ratio be 0.1 to 2.The cationic copolymer of certain minimum is needed to make emulsion-stabilizing, and needs it to provide
Emulsion droplet with certain charge level, certain charge level in later step 2) in formed and at least partly react
The shell of precursors of inorganic oxides is related.The amount of copolymer excessively high (i.e. relatively low amounts of compound A) can be reduced by obtained
The potential porosity level being capable of forming in the coating layer that composition obtains.Therefore, mass ratio C/A is preferably at least
0.15,0.2,0.3 or 0.4, and at most 1.5,1.2,1.0,0.9,0.8,0.7,0.6 or 0.5.
If desired, in the method according to the invention, other of low molar mass can be added in step 1)
Conventional surfactants, to assist forming the drop dispersed and further stablize lotion obtained.Used surface-active
Agent can be non-ionic, cationic or anion or combinations thereof.Preferably, without using surfactant or using only few
Measure surfactant, such as 0.1-3, more preferably 0.2-1.5 quality %.
Method of the invention obtains the dispersion (based on total emulsion) with the emulsion droplet of 1-50 mass % in step 1).
According to the following step and purposes, the lotion with wide scope emulsified particles concentration can be prepared.In general, relatively high dense
Degree is that preferably, this to can according to need in a subsequent step further dilute with water or other solvents in step 1)
It releases.Preferably, the dispersion prepared in step 1) includes at least 2,4,6,8 or 10 mass % and the matter of at most 40,30,25 or 20
Measure the emulsion droplet of %.Based on information presented above, those skilled in the art can determine compound A, copolymer C, water
The relative usage of property medium and other compounds optionally used in the method.
The method of the invention dispersion obtained in step 1) has the emulsion droplet of particle size 30-300nm.It can be with
The formation and size of emulsion droplet are monitored by various technologies;Such as pass through Dynamic laser scattering (DLS).In view of using root
AR coating is prepared according to the composition that method of the invention obtains, the variable of methods as described herein above is selected, so that particle ruler
Very little is preferably at least 35,40,45 or 50nm and at most 250,200,175,150 or 125nm (being measured with DLS).
The method of the present invention includes the step 2) of inorganic oxide shell is provided to emulsion droplet, pass through reality of such as getting off
Existing: the lotion obtained in step 1) adds at least one precursors of inorganic oxides, and leading to core shell quality is 0.2 to 25
Organic/inorganic core-shell nanoparticles.In text, core is the summation of compound A and emulsion stabilizer C, and shell is inorganic oxide precursor
SiO2Equivalent." the metal oxide equivalent of precursors of inorganic oxides " refers to by being fully converted into metal oxygen herein
The quality for the oxide that compound converts precursor, such as TMOS and TEOS can be regarded as a SiO2, titanium tetraisopropylate can be regarded as
One TiO2, and aluminum nitrate can be regarded as half of Al2O3.In step 2) according to the method for the present invention, emulsion droplet plays template
Effect, forms shell by the sol particle of the precursor partially reacted on the template.It is this that nothing is formed by sol-gel process
Casing layer has been described in many publications, including referenced in document and these documents cited in the application
Publication.Suitable precursors of inorganic oxides includes metal salt, metallo-chelate and organo-metallic compound (preferably metal
Alkoxide) and their combination.This compound can carry out various hydrolysis and/or condensation reaction in an aqueous medium, with most
End form is at corresponding oxide or mixed oxide.Within the scope of application, silicon (Si) is considered as metal.Suitable metal
Including Si, Al, Bi, B, In, Ge, Hf, La and lanthanide series, Sb, Sn, Ti, Ta, Nb, Y, Zn and Zr and its mixture.It is preferred that
Ground, metal are at least one of Si, Al, Ti and Zr.Preferred precursor includes alkoxy silane, preferably tetraalkoxysilane or
Trialkoxy silane, such as tetramethoxy-silicane (TMOS), tetraethoxysilane (TEOS), methyltrimethoxysilane, methyl
Triethoxysilane, titanium tetraisopropylate, aluminum nitrate, aluminium butoxide, yttrium nitrate and butanol zirconium.This precursor compound can be by part
Ground pre-reaction or prehydrolysis, to form oligomerization species, typically with about 1-20,1-10 or the nano-sized particles of even 1-5nm
(also referred to as sol particle) form.
In a preferred embodiment of the present invention, at least one inorganic precursor includes alkoxy silane, more preferably
TMOS and/or TEOS.Preferably, shell is formed by substantially to be made of the silica (precursor) as inorganic oxide;
Si of the shell for example comprising at least 80,85 or 90 moles of % is as the metal in inorganic oxide, more preferably at least 95 moles of %
Si.
In the method according to the invention, shell is formed by precursor in template for obtain core-shell nanoparticles
What step usually carried out in a mild condition.As mentioned above, aqueous medium may include organic solvent miscible with water,
Such as alcohol, ketone, ester or ether;Preferably alcohol, such as methanol, ethyl alcohol or isopropanol.Water plays the solvent or diluent of composition
Effect, but can also be reacted with precursors of inorganic oxides;Such as it is reacted with alkoxy silane.Therefore, water present in composition
Amount be at least be used for it is this it is desired reaction, such as such as tetraethoxysilane (part) hydrolysis required for amount.?
In the case where going for TEOS complete hydrolysis, composition should include water with the molar ratio of at least 4:1 and Si.
In the step according to the method for the present invention, temperature is not very crucial, and temperature can be become with wide scope
Change, as long as lotion is not destroyed.Mixed degree can be at most 100 DEG C, but usually environment temperature, i.e., from about 15 to 40 DEG C.
Therefore the hydrolysis is exothermic, it is possible that needing to control the temperature in the step using cooling.PH is in 2-6, excellent
In the range of selection of land 3-5 or 3-4.5.An advantage using these conditions is nano particle by usually with the precursor of negative electrical charge
Form and can at least partly be deposited on the outside of the emulsion droplet with opposite charges.In this way, according to reaction condition,
Open or " fluffy " (fluffy) or inorganic oxide (precursor) layer even more compressed can be formed around emulsion particle.
In the method according to the invention, on template droplets by the process that precursor forms shell be under the following conditions into
Capable: the mass ratio of precursors of inorganic oxides and organic formwork makes organic/inorganic core-shell nanoparticles with 0.2 to 25
Core shell mass ratio.Preferably, core shell mass ratio is 0.2 to 5 and specifically 0.2 to 2.It is highly preferred that this method cause core/
The core-shell nanoparticles of shell mass ratio 0.3-2, more preferably 0.4-1.8.It is independent when not including in the method according to the invention
Adhesive when adding step 3), high core shell mass ratio (such as 2 to 25, specifically 4-23) is especially advantageous.This
In the case of, the oxide precursor added in step 2) also plays the adhesive of integration, for this meaning, some oxides
Precursor will form the shell of core-shell nanoparticles, and some oxide precursors can keep unbonded or only very loosely
It can play the role of adhesive in conjunction with nano particle and in ARC preparation.
The change in size of measurement emulsion droplet can for example be passed through by DLS by the process that precursor forms shell in template
To be monitored.Although DLS technology has the shortcomings that it, for example, predominantly detect larger particles and particle size may also because of from
Precursor release compound (such as alcohol, can be adsorbed in core) and changes, but DLS technology be observation hull shape at one kind
Simply and easily method.When emulsification nuclear particle net charge due to the charge opposite with copolymer inorganic oxide
(precursor) and when reducing, hull shape is at may delay or stop.Certain charge level can be kept so that particle keeps dispersion.Due to
Hull shape is at being considered compound and formed, institute by the outer layer of inorganic nanoparticles and the emulsion droplet comprising cationic copolymer
To desirably form open or fluffy structure in an aqueous medium rather than the shell of (as in dry particle) densification.
In an embodiment of the method in accordance with the present invention, it is formed by the structure (such as its density or surface nature) of shell
It can be advanced optimized by such as getting off: extend the reaction time, react with coupling agent or other processing methods known in the art.By
This is formed by the thickness of shell usually within the scope of 1-20nm, 2-10nm.Such as TEM (specifically ultralow temperature-can be used
TEM), the technology of SAXS or SANS assesses the thickness of the shell and its form of core-shell nanoparticles on particle.In view of relatively thin
Shell, the particle size of core-shell particles is in the range similar to the particle size of emulsion droplet.
Using the core-shell nanoparticles for according to the method for the present invention, obtaining dispersion, it is found that it is significantly good its composition is shown
Storage stability and Treatment Stability, it means that compared with other dispersions based on sol-gel process, the composition
Pole is not easy to change viscosity or gel.It has also been found that by evaporating or being diluted with water or organic solvent (such as alcohol), adjustable point
The solid content of granular media;It can greatly improve regulation composition with matched coating apply a possibility that needs.
It according to the method for the present invention preferably further include step 3): at least one polymerizable compound of addition 2-70 mass %
Or polymerizable compound (summation of the quality % based on core-shell particles and adhesive) is used as adhesive.In principle, it is possible to use step
The rapid composition 2) obtained afterwards forms ARC on substrate, shows after dry and optional solidification to substrate surface one
Fixed adhesion level, this is because the further reaction of precursors of inorganic oxides causes, precursors of inorganic oxides is preparing shell
Shi Tongchang will not react completely.Preferably, adhesive is added into AR coating composition in step 3), which can be
At least one inorganic or organic polyhydroxyl compound or polymerizable compound.When forming ARC by composition, adhesive plays film forming
The effect of agent, and so that core-shell nanoparticles is kept together, cause to be formed by coating with improved engineering properties and cause
It is more preferable to the adhesiveness of substrate after drying and/or solidification.Addition adhesive can reduce the hole of the coating by composition preparation
Rate is horizontal.Therefore, in the step 3) of the method for the present invention, the bonding of the mass % of at least 2,5,10,15,20 or 25 is preferably added
Agent;But it uses at most 65,55,50,40 or 30 mass % (summation based on core-shell particles and adhesive).
Suitable organic bond includes various differences well known by persons skilled in the art in the method according to the invention
Polymer and can be thermally cured or radiation-curable (such as UV) curing monomer.Organic bond, especially radiation curable adhesive are logical
Often have the advantages that they can solidify at a temperature of mutually compatible with such as thermoplastic matrix relatively low, it is preferably low
In 250 DEG C, and organic compound A can also be evaporated from nano particle at this temperature hollow particle is formed in situ.It is inorganic
The use of adhesive may be preferably, to lead to improved engineering properties and durability, but be frequently necessary at about 250-900 DEG C
Solidify under high temperature.It is one advantage of the present invention that the method for the present invention allows, those skilled in the art are selected and use can provide certain
A little coating apply the adhesive of desired property.The example for the suitable organic bond that can be used includes free-radical curable
(peroxide or light-initiated) composition, it includes vinyl monomer and with the polyvinyl of unsaturated group, example
Such as acrylate, methacrylate, maleate/vinyl ethers, or in styrene and/or (methyl) acrylate
Free-radical curable unsaturated polyester (UP) or polyurethane.
In the method for preparing AR coating composition of the invention, before suitable inorganic bond includes inorganic oxide
Body, such as metal alkoxide, metallo-chelate, metal salt and its mixture.Suitable metal include selected from Si, Al, Be, Bi, B, Fe,
At least one element of Mg, Na, K, In, Ge, Hf, La and group of the lanthanides, Sb, Sn, Ti, Ta, Nb, Y, Zn and Zr;Preferably metal is
At least one element selected from Si, Al, Ti and Zr.Suitable precursors of inorganic oxides include it is well known in the art can be via water
Solution and/or condensation reaction to react to form those of corresponding oxide compound.(it is of the invention for precursors of inorganic oxides
It is considered in context for example, by hydrolyzing and/or being condensed being polymerizable or in glass, sol-gel or crystallization stage
It is middle to be polymerize) it can be metal salt or organo-metallic compound, such as alkoxide compound, aryloxy compound, halide chemical combination
Object, nitrate compound or sulphate cpd and combinations thereof.Preferred precursor includes alkoxy silane (including halogenated derivative
Object, especially fluoro derivatives), such as tetramethoxy-silicane (TMOS), tetraethoxysilane (TEOS), methyl trimethoxy oxygroup silicon
Alkane, methyltriethoxysilane, fluoric alkoxy silane (such as trifluoro propyl trimethoxy silane), titanium tetraisopropylate, nitric acid
Aluminium, aluminium butoxide, yttrium nitrate and butanol zirconium.It is highly preferred that precursor includes TMOS and/or TEOS.
Precursors of inorganic oxides can be the mixture of precursors of inorganic oxides compound and corresponding inorganic oxide.It is making
When standby composition precursor compound in an aqueous medium partly pre-reaction or prehydrolysis to form oligomerization species (usually with nanometer
The particle form of size) in the case of, this mixture can be generated for example;This is well known mistake in sol-gel technique
Journey.
In another preferred embodiment, the adhesive used in the method for the invention includes different inorganic oxides
The mixture of object precursor is usually formed the inorganic oxide of mixing in this case, is for for example different glass
It is known.In this mixed oxide, various elements connected together by oxygen atom with formed ion network or covalently
A part of network, rather than exist in the form of the physical mixture of different oxides.In the context of the disclosure, mixed nothing
Machine oxide refers to this definition.Being formed for mixed oxide can be for example by assessing the oxygen formed from different components
The variation of the isoelectric point of compound (such as in the form of film layer), or it is true by analytical technology (such as IR and solid NMR)
It is fixed.Nevertheless, this field is got used to defining this mixing by the theoretical amount of the inorganic oxide of existing every kind of metal
Inorganic oxide composition;Such as the aluminosilicate made of Si- oxide precursor and Al- oxide precursor form it is usual
It is expressed in the form of the content of silica and aluminium oxide.In the case where mixed oxide is as adhesive, it is preferable that main
Metallic element be selected from Si, Al, Ti and Zr, second element be selected from Si, Al, Be, Bi, B, Fe, Mg, Na, K, In, Ge, Hf, La and
Lanthanide series, Sb, Sn, Ti, Ta, Nb, Y, Zn and Zr, wherein the molar ratio of essential element and second element is about 75:25 to 99:
1。
Preferably, adhesive used in the step 3) of the method for the present invention includes silica precursor and aluminium oxide or oxygen
Change the mixture of the precursor of yttrium, because the oxide for being formed by mixing shows high resistance to outdoor property or durability.
According to the method for the present invention can also include addition inorganic bond and organic bond combination, thus for example into
One step improves the property of obtained coating, such as anti-pollution characteristic, or enhancing to the adhesiveness of substrate.These adhesives itself can be with
Polymer or network are formed, but can also be reacted jointly.
In one preferred embodiment, in the method according to the invention used in adhesive by least one nothing
Machine oxide precursor composition.
The step of addition at least one helper component can be optionally included according to the method for the present invention, helper component is usual
It is non-volatile or solid component.Be preferably based on the summation of core-shell particles and adhesive, add amount less than 20 mass %,
The helper component of the amount of even more preferably less than 10 or 5 mass %.These components can be added to aid in treatment coating composition
Or influence the other function of the coating formed by composition.The example of helper component include acid, buffer, catalyst, coupling agent,
Surfactant, defoaming agent, chelating agent, slipping agent, thickener and levelling agent.
It is optionally included according to the method for the present invention by removing or adding water and/or organic solvent come adjusting coating combination
The further step of the solid content of object.Be typically below about 20 using AR coating composition prepared by method of the invention,
15, the solid content of 10,5 or even 3 mass %, and minimum solid content be about 0.1 mass %, preferably at least 0.2,0.5 or
1.0 mass %.In the context of the present invention, solid content refers to the total of the component added in addition to compound A, water and organic solvent
With the i.e. summation of copolymer C, precursors of inorganic oxides, adhesive and helper component.
It include organic solvent as defined above and water using composition prepared by method of the invention, water and organic molten
Agent is also referred to as solvent together.The solvent of the coating composition obtained using method of the invention is liquid component, it includes with
Other coating compositions of solubilised state, dispersed or colloidal attitude, therefore also referred to as diluent.The amount of changeable solvent is to obtain
The desired viscosity of coating composition, the viscosity can be relatively low to allow to be easy to be applied on substrate (example in the form of a film
It is such as used as AR coating).Typically, the viscosity of coating composition be at least about 0.6mPa.s, it is therefore preferable at least 1.0 or
2.0mPa.s.According to applied deposition technique, viscosity may be up to 1000mPa.s.Preferably for uniform thin of manufacture thickness
Film layer, viscosity are at most 500mPa.s, 300mPa.s or 200mPa.s.Using known method measurement viscosity, such as using
It is glued especially suitable for the Ubbelohde PSL ASTM IP no 1 (27042 type) of low viscosity range or using Brookfield
Degree meter.It can for example be evaporated by removing solvent or solid content is adjusted by addition solvent.
In one according to the method for the present invention further preferably aspect, change the pH of coating composition obtained extremely
Inorganic oxide and/or its precursor (being present in core-shell particles and/or as adhesive presence) do not react (including at least only
Very slowly react) level, to prevent the agglomeration of core-shell particles and the premature setting of adhesive;In silica precursor
In the case of, preferably change pH to about 2-3 or even less than 2 is (using standard pH electrode in aqueous or alcoholic dispersion
It measures).In this way, the method for the present invention obtains the composition with good Storage property and extended pot-life.For
Adjusting pH, can add inorganic or organic acid, such as nitric acid solution.
Lower than room temperature, be more preferably less than 15 or 10 DEG C but be higher than solidification point at a temperature of store also improve and obtained
The pot-life of the coating composition obtained.
Above-mentioned steps according to the method for the present invention usually carry out under environmental stress, but those skilled in the art will appreciate that
To high pressure (or low pressure) can also be applied.
The invention further relates to the use AR coating compositions obtained according to the method for the present invention described above, including
All combinations and small variation of indicated step, component, feature and embodiment.
On the other hand, the invention further relates to the methods for preparing ARC over the transparent substrate comprising following steps:
By coating composition according to the present invention or the coating composition obtained using method of the invention in base
Material;And
By coated coating layer drying and solidify.
The transparent substrate that coating composition according to the present invention can be coated on can be widely varied, can be organic
Or it is inorganic, and can have a variety of geometries.Preferably, substrate is at least transparent to visible light.Suitable base
Material includes unorganic glass (such as borosilicate glass, soda-lime glass (soda lime glass), glass ceramics, alumino-silicate glass
Glass) and plastics (such as PET, PC, TAC, PMMA, PE, PP, PVC and PS) or composite material (such as laminated product).It is preferred that
Ground, substrate are glass, such as borosilicate glass;Preferably plate glass, such as with smooth or patterned surface floating
Method glass.
Coating composition of the invention can not only be applied directly on substrate, and can be applied to and be present in
On another coating on substrate, for example, basic ion barrier layer, adhesion promoting layer, hard coating layer or have (higher than substrate) more
The layer of high refractive index.
More than one coating can be also coated according to the method for the present invention, preferably after applying each coating among progress
It is dry.In some embodiments, intermediate drying and curing is carried out after applying some or all of coatings.
In the method according to the invention, a variety of deposition techniques known to technical staff can be used to apply AR coating composition
It applies and manufactures thin homogeneous coating on substrate.Suitable method includes spin coating, dip-coating, spraying, roller coating and folder slot die
(slot die-coating), aerosol coating etc..Preferred method is dip-coating, roller coating and folder slot die.To be coated is wet
The amount and the phase after subsequent drying and curing that the thickness of coating layer depends on the solid film-forming components in coating composition
Hope thickness degree.Technical staff will according to circumstances select appropriate method and condition.
Preferably, coating composition is coated on substrate to manufacture single layer AR coating, the wet thickness with following wet thickness
So that it is dry and/or after solidify will generation about 20nm or thicker thickness, it is preferable that solidify coating after coating with a thickness of
At least about 50 or 70nm and at most about 200,180,160 or 140nm.In case of multilayer coatings, those skilled in the art can
Select different thickness degree.
In coating method according to the present invention, the step of coating composition coated by drying and curing will include: dry
Dry extremely evaporation at least partly solvent and other volatile components (including compound A), are then cured to adhesive and are completely reacted to
For such as inorganic oxide, and optionally removes remaining volatile matter and optional fixedness organic component and (such as be copolymerized
Object);Depending on solidification temperature.
Preferably, it is dried under environmental condition (such as 15-30 DEG C), but also can use high temperature and (such as be up to about
250 DEG C, more preferably up to 100,50 or 40 DEG C) shorten total drying time.It can be by using inert gas or reduction pressure
To promote drying.Based on component to be evaporated, those skilled in the art can determine specific drying condition.
In drying, compound A and/or organic solvent included in the core-shell particles of dispersion can be by least partly
It removes, to generate porous or hollow particle.A specific advantages of the invention are to prepare at relatively low temperatures
AR coating allows to using the substrate (such as plastic basis material) with limited heat resistance.This mode is carried out of the invention
Method can also carry out curing schedule at a temperature of mutually compatible with substrate.After solidification, result in porous coating simultaneously
Show the substrate of AR property.
Preferably, solidify coated layer (after substantially removing volatile matter) after the drying.Can be used a large amount of technologies into
Row solidification, including heat cure, quickly heating, UV solidification, electronic beam curing, induced with laser solidification, γ radiation curing, etc. from
Daughter solidification, microwave curing or combinations thereof.Condition of cure depends on the curing mechanism and substrate of coating composition and adhesive
Type.Technical staff can select suitable technology and condition.For precursors of inorganic oxides is as adhesive, in example
Heat-curable coating at a temperature of being such as higher than 250 DEG C is preferably that this leads to for example better engineering properties.This condition for
It is often infeasible for hardened plastic substrate in an oven;And it does not need to generate AR coating composition of the invention and be had
There is desired porosity level.If hot setting be it is desired, can advantageously with surface heating techniques such as quickly plus
Heat is minimized with exposing the substrate to the time of high temperature, as described in such as WO2012037234.
In a preferred embodiment for operating method of the invention, solidification is at most 300 DEG C, more preferably up to 250
Or carried out at a temperature of 200 DEG C.After solidify coating, can further remove optionally by known method includes copolymer
The remaining organic matter of C;Such as by exposing the coat to solvent and extracting organic compound from coating.
Alternatively, especially in the case where inorganic bond and glass baseplate, can by from about 250 DEG C to 900 DEG C, it is excellent
Heating and continuous at least a few minutes at a temperature of selection of land is higher than 300,400,450,500,550 or 600 DEG C, to be solidified.In height
This kind of compound will be removed in this heating of the decomposition temperature of organic compound or polymer, leads to porosity, and promote nothing
Machine oxide precursor forms oxide, especially when oxygen is present;To lead to solidify and remove organic matter by calcining.?
In the case where unorganic glass substrate, it can be solidified at relatively high temperature;Its softening temperature for being up to glass.It is preferred that
Ground carries out this solidification by heating in the presence of air, is commonly referred to as firing in such as glass industry.Such as fruiting period
If prestige, air may include the water (steam) of increment to further enhance the formation of solidification and inorganic oxide coating.Typically,
The product obtained by this method is complete inorganic porous coating.
In another preferred embodiment of coating method of the invention, this curing schedule and glass tempering are walked
Rapid combination, i.e., will be heated to about 600-700 DEG C by painting glass baseplate in a few minutes, then quench, to generate the steel of coating AR
Change glass or safety glass.
The invention further relates to the AR by that can obtain or obtain according to the method for the present invention to be coated with transparent substrate, such as above
Described, the method includes all combinations and small variation of indicative character and embodiment.
Antireflection (AR) coating or reduction optical reflection coating are such a coatings, can be reduced in 425nm and 675nm
Between one or more wavelength at light from the reflection of substrate surface, as measured under 5 DEG C of incidence angles.To be coated and
Coated substrate does not measure.Preferably, reflection reduces about 30% perhaps more more preferably about 50% or more,
More preferably about 70% perhaps more even more preferably about 85% or more.=100 are reduced with the reflection of percentage expression
× (the not reflection of the coated substrate of the reflection-of coated substrate)/(the not reflection of coated substrate).
Typically, the AR substrate to be coated that can be obtained by means of the present invention shows extraordinary AR property, simultaneously
It is combined with good mechanical performance, such as the wearability by the test of felt defined in EN1096-2 (felt test).Root
Minimum 2% or less is being reflected by apply that side shows under certain wavelength according to AR substrate to be coated of the invention, it is therefore preferable to
About 1% or less, more preferably at most about 1.4,1.2,1.0,0.8 or 0.6% (for two sides substrate to be coated).For two sides
For substrate to be coated, the average reflection in 425-675nm wave-length coverage is preferably about 3% or less, more preferably extremely
More about 2,1.8,1.7,1.6 or 1.5%.
AR substrate to be coated according to the present invention can be used for many different applications and terminal and use, such as window glaze, too
The protection glass or video screen and display of positive energy battery component (including heat solar system and photovoltaic solar system)
Protection glass.Therefore, the invention further relates to include the product using the AR substrate to be coated obtained according to the method for the present invention.This
The example of kind of product include solar panels (such as heat solar plate or photovoltaic module), monitor, mobile phone touch screen show
Device, tablet computer or integrated PC and television set.
The invention further relates to the methods for preparing organic-inorganic core-shell structure copolymer or inorganic hollow nano particle.More specifically, this hair
It is bright pay close attention to the method for preparing organic-inorganic core-shell particles comprising the described above antireflective coating compositions that prepare
Step 1) and 2), including all preferred embodiments.This method can also include the separation nanometer from dispersion obtained
The step of grain;Use any method as known in the art, such as filtering, freeze-drying or spray drying technology.
The invention further relates to the methods of preparation hollow inorganic nano particle comprising preparation antireflection described above
The step 1) of coating composition and the further step for 2) and from core-shell nanoparticles at least partly removing core or template, with
Obtain porous or hollow core (being referred to as hollow core for the sake of simplicity).Organic core may include compound A, organic solvent, copolymerization
Object C and optionally other surfaces activating agent.This core can be partially removed by such as getting off: evaporating volatile component;And/or
Solvent extraction or etching, thermal degradation, catalytic decomposition, light degradation, electron beam or laser irradiation and combinations thereof;Optionally then evaporation
Catabolite.The method of the present invention can also be included the steps that from separated dispersion nano particle obtained;It makes in this field
Known any method, such as filtering, freeze-drying or spray drying technology.Nuclear material can (partly or almost) be removed,
And nano particle is still within discrete form, and divides when from separated dispersion particle for then applying or from dispersion
From particle for being also such after then applying.
The invention further relates to using the method described in the present invention obtain organic and inorganic core-shell nanoparticles or it is inorganic in
Empty nano particle is related to the different purposes of the composition comprising this nano particle and the nano particle and composition.It adopts
It is the organic and inorganic particle or hollow inorganic nano particle mixed with the product obtained according to the method for the present invention, to disperse shape
Formula or as dry nano particle.It was found that the product of dispersion shows significantly good storage stability and Treatment Stability, this
Mean compared with other dispersions based on sol-gel process, which is not easy to change viscosity or gel.Also send out
It is existing, the solid content of dispersion can be adjusted by evaporating or diluting, dispersion obtained can be greatly improved largely not
With possibility used in application.
Using nano particle prepared by method of the invention usually have at most 300nm, more preferably up to 250,200,
The particle size of 150 or 100nm.Preferably particle size is preferably at least 35,40,45 or 50nm.For according to the present invention
Coating composition nano particle for, the size and shape of single core-shell nanoparticles can be very big with difference.Therefore, it
It is emphasised that: it is as discussed above, particle size herein refer to through dynamic light scattering (DLS) in dispersion
The Z average hydrodynamic diameter measured on Malvern Nano ZS.
The invention further relates to the compositions of the nano particle comprising obtaining according to the method for the present invention;And the nanometer
The different purposes of grain and composition, and the product comprising the nano particle and composition or by the nano particle and group
Close product made of object, including paint composition, cosmetic composition, controlled release drug and composite material.
Through the description and claims of present specification, word "comprising" and " containing " and its variant (such as wrap
Include) indicate " including but not limited to ", and be not intended to (and not) exclude other parts, additive, component, integer or step.
Through the description and claims of present specification, unless context requires otherwise, odd number covers plural number.Especially
Ground should be understood to consider plural number and odd number using file in place of indefinite article unless context is required otherwise.
It is unless otherwise stated or clearly contradicted, described feature, integer, feature, compound, chemical part or change
Group should be understood can be applied to described herein together with special or preferred aspect, embodiment or embodiment of the invention
Any other aspect, embodiment or embodiment.
The present invention will be further illustrated by following embodiments and comparative experiments, but the present invention is not limited thereto.